Varnishes and other like materials and process for producing same.



I menses.

PATENT ALFLED WALKER AND FRANKLIN P. WALmR, CINCINNATI, OHIO, ASSIGNORSOE ONE-HALF TO WILL-mil. R. WOOD, OFF CINCINNATI, OHIO.

VARNISHFES AND OTHER. HIKE MATERIALS AND PROCESS FOR PRODUCING SAD/IE.

life Drawing.

To aZZ whom it may concern Be it known that we, ALFRED B. WALKER andFRANKLIN P. WALKER, both citizens of the United States, residing atCincinnati, in the county of Hamilton and State of Ohio, have inventedcertain new and useful improvements in Varnishes and other likeMaterials and Process for Producing Same, of which the following is aspecification.

@ur invention relates to the production of a varnish base, as well astothe production of a new varnish, of which said base is an ingredient.

This new varnish is stable in character, suitable for all of theindustrial uses to which varnishes are applied, and it may also becombined with pigments to make what are commonly known as lithographersinks.

So far as we are aware, the varnishes in common commercial usage forsuch purposes comprise a primary resinious base, which has inherentlycertain undesirable physical characteristics, which are eliminated in mynew varnish.

It is therefore broadly the object of this invention to produce asubstitute for a resinous varnish base, which will retainall of thedesirable or necessary varnish characteristics. and which will not havethose undesirable properties inherent in a varnish formed of a resiniousbase.

This invention comprises not only the varnish and the varnish base, asnew articles of manufacture, but it comprises the process involved inmaking the same.

The particular object of this invention is to provide a substance or aseries of substances replacing the several gums or fossil resins used inpreparing varnishes, readily soluble in turpentine (oil of turpentine),in the volatile products of petroleum and in other solvents of oils andfatty bodies, the solutions having the consistency and flowing qualitiesof varnishes as now used for a variety of purposes.

Regardless of' price values, varnishes as now made and used have certaininherent defects among which the following are the most conspicuous:VVill not mix with dry colors containing lead carbonate without themixture hardening. Lose luster after ex posure to climatic influences.Frequently sag and flow after having been applied.

Specification of Letters Patent.

Patented Mar. 9, 11915.

Application filed October 31, 1910. Serial 1%. 590,036.

Frosting in extreme cold weather. Blooming by exposure to a dampatmosphere or to water. Cracking by expansion or contraction due toalternation of heat and cold. Darkening in color after being applied.Solubility (partial) in alcohol, after applying and drying. We havefound it possible to substantially eliminate these defects by avoidingthe gums and resins as now employed, and using therefor a. product madefrom a base comprised of a combination of a metallic soap with ametallic oxid, and soluble in appropriate varnish oils.

In searching for one of the ingredients of the primary base designed toact as a substitute for resinous bodies, we found that a substance knowngenerically as aluminum soap possessed certain desirable characteristicsas a physical substance, as well as the necessary chemical peculiaritiesfor entering into combination with the other ingredients constitutingwhat we have designated as a primary varnish base.

A specific example of an aluminum soap, and the process of preparing itis as follows :We boil together, say linseed oil, with caustic soda,until the alkali has been absorbed, combined with, and neutralized bythe fatty acids. To this neutral body, we then add the double sulfate ofaluminum and soda, that is common alum. This yields a precipitatedproduct which may be identified as a linoleate of aluminum, or aluminumsoap. This product, when isolated and cleaned is found to be a gummy,plastic body, having luster, drying properties, and other qualitiesdemanded in a varnish base, but unlike a resinous body, this aluminumsoap is of uniform consistency, stable in character, elastic, and has asuperior luster. In fact, we have discovered that various other metallicsoaps formed from the metals of the aluminum group, are also availableas ingredients for the varnish base, and we do not desire to be limitedto the aluminum soap except where the same is specifically claimed.

The metals for forming the metallic soap with which we have produced thebest results are chiefly aluminum, iron and chromium, which appear tohave the same properties for this purpose, but render slightlydifferentcolored varnishes. The aluminum soap is, however, almostcolorless, and therefore peculiarly suitable for lighter varnishes Whereno staining is desired, and also on account of its colorlesscharacteristic, it forms a most suitable medium for the mixing ofpigments, Where lithographers ink is to be produced. These metallicsoaps are also readily soluble in turpentine, ,or other analogouscarriers commonly used as varnish ingredients, such as coal tar benzol,carbon tetrachlorid, kerosene and the like.

If we desire to manufacture the varnish direct, the next step is todissolve, say, the

aluminum soap in the oil of turpentine, or 1 its equivalent. The productthus formed is a gelatinous substance, of viscous consistency,substantially colorless, and possessed of desirable varnish makingcharacteristics, without the undesirable characteristics of resinousvarnishes, while it has certain additional and valuable characteristics,new in varnishes, which will be later detailed. The function of thissolvent is that of a medium for bringing the metallic soap into intimatecontact with the other component from ,Which the primary liquid varnishis formed. To incorporate this jelly-like aluminum soap into suitableliquid varnish form of proper consistency, we next combine it with ametallic oXid in the presence of water. An instance of such metallicoxid is magnesium oxid, which will combine with or dissolve into thesolution of aluminum soap if they are heated together in the presence ofwater. Preferably however, we use hydrated oxids of alkaline earthmetals, such as hydrated oXid of calcium. Whereas the normal metallicsoaps of most of the metals,

are neutral bodies, We have discovered that the metallic soaps of thealuminum group of metalshave acid characteristics, in fact, they exhibitthe characteristics of a single acid in their reactions, and, therefore,this component seemingly has the capacity of entering into a chemicalcombination with any metallic base, accepting the conventionaldefinition of a metallic base as an element or combination thereofcapable of chemical reaction with an acid. The term metallic base istherefore of generic significance, whereas, the term an oxid of thealkaline earth metals has specific significance. In practice, we havefound that the metallic soaps, characterized by this acid reaction,yield the best results when combined with members of the .alkaline earthgroup of metals, or the oxids or hydrates thereof. For instance, amagnesium oxid or a calcium or barium hydrate yield substantially likeproducts, dillering slightly in color characteristics. A liquid varnishthus formed is primarily characterized by an absence of resinoussubstances and it is formed by a chemical combination of a metallicsoap, or a solution thereof, having an acid reaction,

aluminum group of metals will not,

commercial varnish of. the desired consistency.

The hydrated calcium oXid of course contains the Water of chemicalcombination, and in a dry powdered consistency, it is heated With thesolution of aluminum soap.

A remarkable physical transition takes place, that is, the jelly-like,turpentine solution of the aluminum soap enters into a liquid solutionWith the hydrated calcium oxid, constituting one of the species of theliquid varnishes which it is the object of this invention to produce. Wehave also reached the conclusion based upon analytical and research Workthat a chemical reaction takes place, the union resulting in a colorlessrelatively thin liquid which is a superior varnish when the Water hasbeen eliminated by evaporation. This liquid frequently co'ntams someimpurities in the nature of silicious matter from the lime, andoccasionally some carbonates, so that we preferably filter the liquid toobtain a clear,

fixed varnish.

This varnish is so light in color that it isdesirable for wood-Work, orother charac- 'ters of varnishing in which a minimum of staining effectis desired. For preparing a varnish to be combined with pigments,

that is to say a lithographers ink, we preferably combine. the solutionof aluminum soap with hydrated oXid of magnesium. The varnish thusformed my be generically considered as one product, susceptible ofembodiment in a variety of s ecies, dependmg upon the component oi themetallic soap, as well as upon the metalp oxid component combinedtherewith. us, to produce a series of darker, or staining varnishes, wecan form the metallic soap, say

of a ferric oxid, or chromium oxid, which metallic soaps likewisepossess the capacity physical characteristics and superior varnishqualities. The metallic soaps of the course, combine with or formsolutions with oxids of the same group of metals. The varnish thusformed is stable in character, has superior flowing qualities, and iselastic, so that the varnish does not crack or blister when dried andexposed to the elements. Furthermore, it is of uniform consistency,works Well under the brush, has a high luster when dry, takes on asuperior finish when burnished, is not soluble in alco-' hol when dry,and will not soften or run on exposure after it is dried, and in short,it is not subject to the various physical and chemical changes which arecharacteristic in varnishes formed of a resinous base. It is alsocheaply and easily manufactured.

For some commercial purposes, it is desirable to make a primary Varnishbase as an article of commerce instead of manufac turing the varnishdirect, as above described. Our invention also comprehends this productin process. The advantage of this discovery is, that we can produce aprimary varnish base of condensed form, non-liquidin consistency,containing no inflammable oils, and which can be cheaply shipped toremote points directly to the users, or merchants, so that it can beconverted into a varnish at its destination by simply dissolving it inthe oil of turpentine, or other analogous varnish oil commonlyrecognized as an acceptable substitute therefor. For the purpose ofproducing this article of commerce for such purpose, we directly combinethe metallic soap with the metallic oxid, notatably the hydrated oxidsof alkaline earth metals. For instance, We can combine the aluminum soapdirectly with the hydrated calcium oxid, producing thereby a primaryvarnish base, consisting of a condensed adhesive paste, readily solublein turpentine. For instance, to produce a hundred pound quantity, sixand two thirds pounds of the dry hydrated calcium oxid would be used.This product, irrespective of its diversity of species, constitutesgenerically a primary varnish base just as the varnish, irrespective ofits diversity of species, constitutes generically a liquid varnishproduct.

While the proportion is not of the essence of the discovery, we willdescribe one of the quantitative embodiments of the process, which wehave found to yield best results, and which will suifice to disclose tothose skilled in the art a practical working basis for producing thevarnish. Onehundred pounds of linseed oil is mixed with a solution ofcaustic soda in such amount as to carry 13.7 pounds of sodium hydroxid,the

preferable amount ofwater being between twenty-five and forty pounds.This mixture is heated in a bath of hot water or of steam for two hoursor less. or until the alkali hasbeen entirely absorbed, combined withand neutralized by the fatty acids of the oil. This neutral product isdissolved in water to obtain a dilute solution, preferably weighingabout ten thousand pounds, 2'. 0., containing not over one per cent. ofoil. Sixty to sixty-five pounds of the double sulfate of aluminum andsodium, or other alu or of its equivalent in any water-soluble salt ofaluminum, is dissolved in water to obtain a weaksolution, containingpreferably 0.05% and not above 0.10% aluminum. The oil solution ispoured into the aluminum solution, the mixing liquids being stirredrapidly and constantly during the operation. After the aluminum soap hassettled, the supernatant liquor is drawn off, the soap is washed untilexternally free from the excess alum, then squeezed out thoroughly,suspended in hot water to soften it and kneaded in successive portionsof hot water or until all but traces of the excess of aluminum salts hasbeen removed. The washed soap is freed from waterby squeezing androlling and is then suspended in its own weight or in a sufficientquantity of turpentine, the mixture being heatedand stirred to evaporatethe remainder of the inclosed water. This product is a very viscous orjelly-like solution and is next treated with a pasty or creamy mixtureof 3.6 pounds of magnesia and five to ten pounds of water. By heating,the magnesia dissolves completely in the aluminum soap solution,combining withthe soap to form, after evaporation of the water, a clearsolution, of the consistency of varnish and of similar and superiorflowing qualities. This product can be used in this state," but is bestused after addition to a suitably prepared linseed oil, such as apartially-oxidized or blown oil. I

Other drying, semi-drying or non-drying oils may be used, and may yieldparallel products; in place of magnesia, may be used lime, baryta orstrontia, preferably in the state of dry hydroxid,'or the alkali metalhydroxids, potash and soda, or the oxids of other metals together withwater or as hydroxids, or mixtures of them may replace the magnesia, orthe carbonates of the respective bases may be used. The dry hydroxids ofthe suitable metals are preferable, as solution and combination with thealuminum soap take place most rapidly and completely. It is alsopreferable, when hydrates of the alkali earth metals are used, toevaporate off the water of reaction so as to produce an anhydrousvarnish product.

The quantity of magnesia used in the above formula is that which willcombine with one-half of the total fat acids of the linseed oil to forma normal magnesia soap. We have found, in the case of most of the basesused for the purpose above described,

is of especial advantage when applied to ucts have this composition, theadded hydroxld being in such proportions as to form a normal soap withone half of. the total fat acids contained in the aluminum soap. Butconsiderable variation is possible and in some cases desirable. Thus, inthe instance of potash, the amount necessary to li'quefy the firm,jelly-like solution of one part of aluminum linoleate in one part ofturpentine is suflicient to combine with but one-sixth of the linseedoil fat acids present, while three times this amount can be combined,the products being generically the same, but constituting difierentspecies.

While we have called'this new product a varnish, it has beenfound'useful as an electric insulation as a substitute for oils in themanufacture of paints, and for various other analogous uses.

We have also found by experience and practical working tests inlithographic presses, that these varnishes have a very extensive fieldof utility in the lithographic art. The lighter or colorless varnishes,such as the aluminum soap and calcium oxid product" combine readily withpigments, and the superior working qualities of the liquid t e rollersand stones of presses. It does not penetrate the paper as ordinarylithographers inks do, and, therefore, imparts a high luster and anembossed efiect to the lithographic products.

Of course, we do not limit ourselves to any particular fields ofapplication, the term varnish being used in its generic sense, ascovering various fluids of like general character and usage, such asinks, pigments, paints, stains or enamels.

Having described our invention, we claim:

1. A new article of vmanufacture, consisting of a liquid comprising asolution of aluminum soap with a metallic base.

2. A new article of manufacture, an an- .hydrou's liquid varnishcomprising a solution of aluminum soap with an oxid of an alkaline earthmetal.

3. A varnish product comprising a liquid resulting from the solution ofmetallic soap with a metallic base having the property of entering intosolution therewith, the said substances constituting the essentialvarnish base and said solution being reduced to proper fluidconsistencycby suitable varnish dilutant carrier.

4. A varnish product comprising a liquid resulting from the solution ofan oil, metallic soap, and a base having the properties of dissolvingtherein.

5. A varnish comprising a liquid solution of a metallic soap of aluminumand an oxid of an alkaline earth metal, characterized by an absence oforganic resins or gums.

6. The herein described process of forming a varnish which consists informing a solution of metallic soap with a metallic base, having theproperty of dissolvingtherein and reducing the same to proper fluidconsistency by adding a varnish carrier.

7 A liquid varnish characterized by an 8. A liquid varnish characterizedby an absence of gums or resins, comprising a solution of a metallicsoap of aluminum and a metal of another group.

9. A liquid varnish characterized by an absence of gums or resinsvcomprising a solution of a metallic soap of aluminum and an hydratedalkaline earth metal, the water of reaction having been eliminated toconstitute a substantially anhydrous varnish product.

10. A primary varnish base comprising a solution of a metallic soap ofaluminum with a metallic base, reduced to substantially solid form byevaporation, said product being soluble in a conventional varnishcarrier.

11. A primary varnish base comprising a suitable varnish carrier.

12. A primary varnish base comprising a solution of a metallic soap ofaluminum with a metallic base, reduced to substantially solid form byevaporation and soluble in a suitable varnish carrier.

13. A liquid varnish characterized by an absence of gums or resins, andcomprising a solution of a chemical union of a metallic soap ofaluminumand a base, the metal of which belongs to a group other than thealuminum grou 14. A liquid varnish characterized by an.

absence of gums or resins and comprising a solution of a chemical unionof a metallic soap of aluminum and an oxid of the alkaline earth metals.

15. A liquid varnish comprising a chemi cal union of a metallic soaphaving an acid characteristic, with a metallic base. 16. A liquidvarnish comprising a chemical union of a metallic soap having acidcharacteristics with a metal hydroxid.

17 The process of making liquid varnish which consists in chemicallyuniting a me-- tallic soap having an acid characteristic, with a metalhydroxid, and eliminatmg the water of combination liberated by thereaction.

18. A varnish characterized by the absence of gums and resins, andcomprlsmg a solution of a varnish base consisting of a metallic soap ofa gummy, plastic uniform consistency, having luster, elasticity anddrying properties, and having the property of dissolving readily withvarnish solvents to form a liquid freely [lowing under the brush andinsoluble in alcohol when dry.

In testimony whereof, We have hereunto set our hands.

' ALFRED B. "WALKER.

FRANKLIN P. WALKER. Witnesses OLIVER B. KAISER, EMMA SPENER.

